Water-insoluble mono-azo-dyestuffs and fiber dyed therewith



Patented Mar. 26, 1935 I WATER IN SOLUBLE MONO AZO- DYE STUFFS AND FIBER DYED THEREWITH LeopoldvLaska and Arthur Zitscher, Offenbachon-the-Main, Ernst Fischer, Frankfort-cn-the- Main,

and Wilhelm Lamberz, Leverkusene- Wiesdorf, Germany, assignors to General AnilineWorks, IncqNew York, N. Y., a corpora tion of Delawarev No Drawing. Application August 25, 1933, Serial 7 No. 686,851. In Germany September 9, 1932 'Claims. (e1. zoo-es) The present invention relates to water-insol uble mono-azo-dyestufis andto fiber dyed therewith; more particularly it relates to dyestuffs of the following generaliormulaz;

som

oxy-4-chlorobenzen or with l-(2'.3-hyd'roxye W naphthoylamino) -2-methoxy-5 chlorobenzene.

The following examples serve" to illustrate the invention, but they are not intended to limit it thereto; I i e I:

Dyeing prescriptionjor Ewamplesf1+8 50 grams-of well-boiled cotton yarn are treated at 35 c. to 40 o. with the grounding liquor for 10 v 1 1 e v half-amhour, well freed. from water by squeezing 9 gl i or centrifuging and developed.fdrhalf-an-hour I '3 in the dye bath; the dyed yarn isywell rinsed, x x a soaped at boiling temperature, rinsed-again and 15 dried.

i r 0011i (1) (d) Grounding liquor wherein one X stands for hydrogen and the 6 grams of 1-(2.3-hydroxynaphthoylamino)- 1 other X for methyl, R; means an alkyL'ar'alkyl 2-methyl-4-methoxy-benzene are dis- 20 or a completely hydrogenatedhydroaromatic solved at boiling temperaturein radical, R2 an alkyl, aryl or aralkyl radical, 10 cc. of caustic soda solution of 343.36

We have found that valuable red mono-azo- 10 cc. of Turkey red oil 1:2 and dyestuffs are obtainable by coupling the diazo- 900 cc. of water. The whole is then made up compounds of the bases of the following general with Water to 1000 cc. 25 formula: J H 1 i" R1 (b) Dye bath 7 H sow/A 2.42 grams of Z-amino-toluenei-sulfonie acid diethylamide are diazotized in the usual ,rmannerwith" p y 3.1 cc; of hydrochloric acid 20 B. and t 8 cc, of sodium nitrite solution 1:10. The wherein R1 represents an alkyl, aralkyl or a comg Solution lsbthen rendefred neutral, pletely hydrogenated hydro-aromatic radical, R2 79 o ongo'paper Y F O v 1 cc.of sodium acetatesolutmn 1.5, an. alkyl, aryl or aralkyl rad1cal,w1th 1-(2 .3 140 cc of Sodium h i c loride solution 1.5 are hydrexynaphthoylammo) 4: methoxy-benzenes added d the hole made u with which are further substituted in the orthoor i y a 5 7 meta-positionto the methoxy group by a methyl co er n 7 s upfpr vid d t at th dia -c mp n nts d There is obtained a vivid red dyeing of very 40 t ntain any s u z r up su for good fastness to Washing, to chlorine, to boilinginstance, the sulfonic or carboxylic acid group. lye and especially to light. The d w he dyestuffs may be p duced in kn w i sponds to the following formula: ner in substance, on the fiber or on" anyof the '1 e usual substrata adapted for theproduction of 0235 lakes; when produced on' the fiber, they yield I vivid shades of verygood fastness properties.

The dyestuffs of the present invention are distinguished by an essentially better fastness to light than the'azo-dyestufis obtainable according to the statements of the U. S; Patent No. 1,678,-

599 by coupling diazotizedl-amino-fi-methylbenzene-3-sulfonic acid amides with 1-(2.3- hydroxynaphthoylamino) -4-ethoxybenzene, 1- (2'.3'-hydroxynaphthoylamino) 3 methylbe zene, 1- (2 .3-hydroxynaphthoylamino) -2-meth- 5'0 described in Examples 1 and 2.

(2) (a) Grounding liquor 5.5 grams of 1-(2.3-hydr0xynapthoylamino) 3 methyl .-*4 methoxy benzene, are dissolved at boiling temperature with 10 cc. of caustic soda-solution of 34 B., 10 cc. of Turkey red. oil 1:2 and 900 cc. of water. The whole is then made 7 up with water to e 1000, cc. p (b) Dyebath 2.9 grams of 2-amino-toluene-i-sulfonic acid-Nemethylj-benzyl-amide are di- I azotized in the usual manner with 3.1 cc. of hydrochloric acide of 20 B. and

8 cc. of sodium nitrite solution 1:10. The

dia'zo-solution is then rendered neu- 'tral to Congo-paper by means of 72 cc. of sodium acetate solution 1 :5, f 140 cc of sodium chloride solution 1:5 are 1 added. and the whole is made up with V :1 coldwater to I '1. 100.0 cc:

There is obtained a yellowish-red dyeing of very good fastness to washing, to chlorine, to

Y "boiling-lye and especially to light. The dyestufi corresponds to the followingformula:

I 0H; 7 V

(3) 0a) Groundin liquor scribed in Example 1-.

(w-mm" V 3.0'6"gramsf of 2-amino-toluene-4-sulfonic -acid-N methyl+orthoeanisidide are dia'zotized as There is obtained a red dyeing of good fastness properties. V v

V (4'). (a) Grounding liquor The grounding liquor is prepared as that described in Example r g w Dye bath v 2.82igrams of 2T-amino-to1uene-4-sulfonic acid N-methyl-cyclohexyl-amide are diazotized as described in'Exam'ples-l and2. l I 7 There is obtained a red dyeing of good fastness properties. l

5) (a) Grounding liquor 6 grams of l 4 (2'.3' hydroxynaphthoyl amino)- 2 methyl 4 methoxy benzene are dissolved at boiling temperature in V cc. of caustic soda solution of 34 B.,

10 00. of Turkey red oil 1:2 and V 900 cc. of water. The whole is then made up with waterto 1000 cc.

(b) Dye bath 3.66 grams of 2-amino-toluene-4-sulfonic acid dibenzyl-amide are dissolved in V 20 cc. of acetone and v l 3.1 cc. of hydrochloric acid of 20 B.;' the whole is then diazotized with 8 cc. of sodium nitrite solution 1:10, a small quantity ofwater is added and.

the diazo-solutio n is rendered neutral to Congo-paper by means of '72 cc. of sodium acetate solution 1:5. The

whole is then madeup with water to i There is. obtained a vivid yellowish-red dyeing of very good fastness to'washing.to'chlorine; to .boilingelye and especially to light. j H

(6) (a) Grounding liquor (b) mt ham 1 3.52, grams of Z -aminmtoluene-4-sulionic acid N-benzyl anilide. are dissolved cc. of acetone and 10 3.1 cc. of hydrochloric acidof Be.

8 grams of ice are thenadjded and the whole is diazotized with 8 cc. of sodium nitrite solution 1:10. The diazo-solution is then'rendered neutral to Congo-pap'erby means of '72 f cc. of sodium acetate solution 1:5, 140 cc. of sodium chloride solution1z5 are added andthe whole is made up.

with cold water to I V 1000 cc.

'7 There is obtained very good fastness properties.

A 7) (a) Grounding liq The grounding liquor is prepared: as that de-f' scribed in Example-5r I I r (b) Dye bath 1 3.58 grams of 2-amino-toluene-4 sulfonic fa. vivid scarlet dyeing of V acid-N-cycloliexyl-benzyl-amide are dissolved in.

There is obtained a vivid yellowish-red dyeing v of very good fastness to washing, to chlorine, to boiling-lye" and especially' to light. (s an Groun ing liquor I amino) -.3methyl 4 miethoiq -ben- 'zenear'e dissolved at boiling tempera- .turein cc. oi caustic soda solution 01 34 B.;

10 cczof Turkey red oil 1:2 and. 900" cc. of water. The whole is-thenimade up with water to. V T r 1000' -cc. I I J:

,zclairnsadonot: containeany;substituentswhich are -('b) Dyetbath' 3.44 grams of"2-amino tolueneeesulfonic acid- "N cyclohexylanilide aref diaz o'tized as described in Example '7.

There is obtained a yellowish-red dyeing of good fastness properties;

(9) 14.5 grams of 2-amino-Etoluene-4-sulfonic acid-N-methyl-beniyl-amide are 2 diazotized in the usual manner. Thereupong- 'the diazo-solution to which sodium acetate has been added in such a quantity as is necessaryhfor binding the excess of hydrochloric acid is introduced, while stirring, into a solution of 15.35. grams'of 1-(2'.3'-'

hydroxynaphthoylamino) -'3 '-methyl-4- methoxybenzene in dilute caustic soda' solution.

yield recl tints which are ,fast to light Y (10) 17.6 grams of 2-amino toluene l sulfonic acid-N-benzyl-anilide are diazotized as described in Example 6. Thereupon, thedia zo solutionfto which sodium acetate.,has beerr addedin 's uch a quantity as is necessary for binding therexcess ofrhydrochloric acid; isintroduced, while stirring, into a solution of 15.35 gramsp-of '1-- 2.3".-hydroxynaphthoylamino) 2 -methyl--fl .-methoxybenzene -in dilute caustic soda solution. v,

The-dyestuif whiclrhas been precipitated is filtered by suction; well washed and dried. It forms a red powder. The: lakes prepared from the dyestuff in the usual "manner yield are fast to light.

The coupling may also be effected in the presence of a substratum adapted for theproduction of lakes. The dyestuffs are especially adapted for dyeing rubber goods, since they are fast to vulcanization.

The following table indicates a number of other azo-dyestuffs obtainable according to the present invention:

red tints WhiChI'5;

known to render organicz'compounds-rsoluble in water or alkalies andto tend to depreciate the fastness of the dyestuifs to alkalies. Substituents of this kind are-,for instance, the sul-., fonic acid and the; carboxylic acidsgroup.

We claim:

l. The water-insoluble mono-azo-dyestuffs'of the following general formula:

SO2.N

when produced on the fiber, vivid red dyeings of very good fastness properties; particularly of very good fastness to light.

2. The water-insoluble mono-azo dyestuffs of the following general formula:

Diazo-compound from 2-an1in0-toluene-4-sulfonic acid- Coupled with 1-(2.3-hydroxynaphtl1oylamino) Tint 1 Dimethylamide. 2-methyl-4-methoxy-benzene Vivid yellowish-red.

2 Do 3-111ethyl-i-methoxy-benzene 1 Do. I

3 Dipropylamide. 2-methyl-4-methoxy-benzen Vivid scarlet.

4 Dibutylamide Vivid yellowish-red.

5 Diamylamide 0. Do.

6 Methyl-ethylamide 3-metl1y1-4-methoxy-benzene Do.

7 l\4[ethy1-ethanol-amide Z-methyM-methoxy-benzene. Do.

9 Methyl-allyl-amide. 3-methyl-4-methoxy-benzene. Vivid scarlet. l0 Methyl-propylamide. Z-methyl-l-methoxy-bcnzene Do. 11 D0 n 3-meth -4-methoxy-benzene .4 Do. 12 Methyl-butyl-amide 2-methyl-4-methoxy-benzene. V vid yellowish-r d. 13 Methyl-isobutyl-a ide o Vivid scarlet. 14 Do 3-methyl-4-methoxy-benzene Do. 15 N-methyl-benzyl-amide z-methyl-i-methoxy-benzene Vivid medium red. 16 N -ethyl-benzyl-amide o Vivid bluish red. 1 17 D0 3-methyl-i-methoxy-benzene Vivid yellowish-red. 18 Z-methyl--methoxy-benzene Vivid medium red. 19 o Vivid yellowish-red. 20 S-methyl-i-methoxy-benzene Vivid scarlet. 21 2-methyl-4-n1ethoxy-benzenc Vivid yellowish-red. 22 1 1 3-methy1-4methoxy-benzene Do. 23 N-methyl-(para-1nethoxy)-benzy amide o Vivid l t 24 D 2-111ethyl-4-methoxy-benzene Vivid yellowish-red, 25 N-methyl- (ortho-chloro) -benzyl-amide dc Do. 26 Do.. A 3-methyl-l-methoxy-benzene D0. 27 rln I Vivid bluish-red. 28 2 rr1 ethyl--methoxy-benzene g Vivid yellowish-red. 29 d0 D 0 30 Scarlet. 31 Do. 32 'Vlvid yellovlishied. 33 Dibenzyl-amide Scarl V Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended wherein one X stands for hydrogen and the other X for methyl, R1 and R2 mean alkyl or aralkyl radicals, yielding, when produced on the fiber, vivid red dyeings of very good fastness properties, particularly of very good fastness to light.

and R2 an alkyl, aryl or aralkylradical, yielding} '3; The" water-insoluble mono-azo-dyestufi of the following formulaf V 5 SO z.N V

i CHLCH N H N I -OH cm a y COVNHIC 'OCH: '15 yielding, when produced on the fiber, a vivid I yellowish-red dyeing of .very good fastness to washing, chlorine, boiling-lye and to light. v 4. The water-insoluble mono-azo-dyestufi of 20 the following formula:

V v 02H;

' SOLN 0H,.C5H5

OH OH;

yielding, when produced on the fiber, a vivid yellowish-red dyeing of very good Iastness to washing, vchlorine, boiling-lye and to light.

5. The water-insoluble mono-az'o-dye'stufi of the following formula:

som

yielding, when produced on the fiber a" vivid yellowishred "dyeing washing-"chlorine, boiling-lye and to light.

6, Fiber dyed with claimed in claim-1.

of very good 'tastness to the .morio-azo-dyeet ifie as V LEoPoLDLAsKAf ARTHUR ZITSCHER. ERNST FISCHER. LAMBERZ 

